The radiative lifetime of the <sup>1</sup>D<sub>2</sub> state of Ca and Sr: a core-valence treatment
C W Bauschlicher Jr; S R Langhoff; H Partridge; C W Bauschlicher Jr; NASA Ames Res. Center, Moffett Field, CA, USA; S R Langhoff; NASA Ames Res. Center, Moffett Field, CA, USA; H Partridge; NASA Ames Res. Center, Moffett Field, CA, USA
Журнал:
Journal of Physics B: Atomic and Molecular Physics
Дата:
1985-04-28
Аннотация:
Theoretical studies of the lowest <sup>1</sup>S, <sup>1,3</sup>P and <sup>1,3</sup>D states of calcium and strontium are presented. The excitation energies, dipole-allowed transition moments and the <sup>1</sup>D-<sup>1</sup>S quadrupole moment are studied as a function of the one-particle and molecular orbital bases and level of correlation treatment. Including core-valence correlation significantly reduces the magnitude of the dipole and quadrupole transition moments, producing oscillator strengths that lie within the experimental error bars. On the basis of relativistic effective-core potential calculations, the authors find that, unlike barium, the strontium transition moments are not significantly changed when relativistic effects are included. Spin-forbidden transitions were assumed to occur entirely as a result of the breakdown of LS coupling. The magnitude of the singlet-triplet mixing was determined both by ab initio calculation and from the observed deviations from the Lande interval rule. The calculated <sup>1</sup>D<sub>2</sub> state lifetime for Ca is 3.1+or-0.3 ms, which is in reasonable agreement with the experimental value of 2.3+or-0.5 ms (with an absolute upper bound of 4 ms). The dominant decay mechanism is spin-forbidden dipole-allowed transitions, with only 12% arising from quadrupole transitions. Similarly for the <sup>1</sup>D<sub>2</sub> state of Sr, the authors compute a radiative lifetime of 0.49+or-0.04 ms with only 2% of the decay from quadrupole transitions.
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